Polymers made from bis(2-hydroxyethyl)isosorbide and enduses thereof

ABSTRACT

This invention provides a new, biomass-derived glycol, bis(2-hydroxyethyl)isosorbide, which is found to be a valuable monomer for a wide variety of polymeric materials

FIELD OF THE INVENTION

[0001] This invention provides a new, biomass-derived glycol,bis(2-hydroxyethyl)isosorbide, which is found to be a valuable monomerfor a wide variety of polymeric materials.

TECHNICAL BACKGROUND OF THE INVENTION

[0002] There is a desire to utilize polymeric components ultimatelyderived from biomass. The diol 1,4:3,6-dianhydro-D-sorbitol, hereinafterreferred to as isosorbide, is readily made from renewable resources,such as sugars and starches. For example, isosorbide can be made fromD-glucose by hydrogenation followed by acid-catalyzed dehydration. Thepreparation of isosorbide is known within the literature in, forexample, G. Fleche, et. al., Starch/Starke, 38(1), pp. 26-30 (1986).Isosorbide has the additional advantage of increasing the heatresistance of a polyester into which it is incorporated by raising-itsglass transition temperature (Tg).

[0003] Charbonneau, et. al., in U.S. Pat. No. 6,063,464, describe aprocess to produce polyesters which incorporate isosorbide, that have aninherent viscosity of at least 0.35 dL/g when measured as a 1%(weight/volume) solution of the polyester in o-chlorophenol at atemperature of 25° C. They generally teach the use of aromatic andalicyclic diacids. A shortcoming found in this disclosure was the lowincorporation rate of the isosorbide monomer. Of the 16 preparativeexamples included within this disclosure where the percentage ofincorporated isosorbide into the polymer could be assessed, theincorporation level of added isosorbide monomer into the as producedpolymer ranged from 12 to 70 percent. The average incorporation rate ofadded isosorbide monomer into the polymer was disclosed to be 48percent. As one skilled in the art would appreciate, this inefficiencyof isosorbide monomer incorporation into the polymer leads to complexglycol recovery and separation processes.

[0004] The present invention overcomes this shortcoming and provideschemically modified isosorbide derivatives which allow for essentiallycomplete incorporation into high molecular weight polymers derivedtherefrom. The essentially complete incorporation of isosorbide allowsavoidance of complex glycol recovery and separation processes.

[0005] The present invention provides valuable polymeric materials, suchas polyesters, polyamide esters, polyurethanes and polycarbonates whichincorporate said chemically modified isosorbide derivatives.

[0006] One aspect of the present invention includes1,4:3,6-dianhydro-2,5-bis-O-(2-hydroxyethyl)-D-sorbitol, hereinafterreferred to as bis(2-hydroxyethyl)isosorbide. Heretofore,bis(2-hydroxyethyl)isosorbide has not been reported within the art.Similar derivatives of D-mannitol have been reported.1,4:3,6-dianhydro-2,5-bis-O-(2-hydroxyethyl)-D-mannitol, hereinafterreferred to as bis(2-hydroxyethyl)mannitol, has been prepared as anintermediate in the preparation of crown ethers. For example, Ashton,et. al., in Eur. J. Org. Chem., (5), pp. 995-1004 (1999), reported thepreparation of bis(hydroxyethyl)mannitol for use in the preparation ofcrown ethers. El'perina, et. al., in Izv. Akad. Nauk SSSR, Ser. Khim.,(3), pp. 627-632 (1988) and in Izv. Akad. Nauk SSSR, Ser. Khim., (3),pp. 632-637 (1988), prepared bis(2-hydroxyethyl)mannitol throughbase-catalyzed alkylation of mannitol with2-(2-bromoethoxy)tetrahydropyran, followed by deprotection of thealcohol function. This material was further utilized in the productionof crown ethers. As one skilled in the art would appreciate, the stereo-and regiochemistry of said bis(2-hydroxyethyl)mannitol, which makes ituseful as a precursor for crown ethers, would lead to significant cyclicoligomer formation in the production of the valuable polymeric materialsdescribed herein. Significant cyclic oligomer levels in polymericmaterials are not desirable for most end uses described herein.

SUMMARY OF THE INVENTION

[0007] One aspect of the present invention includes a new composition ofmatter termed bis(2-hydroxyethyl)isosorbide.Bis(2-hydroxyethyl)isosorbide may be prepared through chemicalmodification of isosorbide. Polymeric materials derived frombis(2-hydroxyethyl)isosorbide, such as polyesters, polyamide esters,polyurethanes, polycarbonates, and the like, are useful in a widevariety of shaped articles, such as films, sheets, containers, fibers,molded parts, coatings, foamed articles, and the like.

[0008] A further aspect of the present invention includes polyesterswhich incorporate bis(2-hydroxyethyl)isosorbide. Said polyesters whichincorporate bis(2-hydroxyethyl)isosorbide are comprised essentially of45.0 to 50.0 mole percent dicarboxylic acid component, 50.0-0.1 molepercent bis(2-hydroxyethyl)isosorbide, 0 to 49.9 mole percent of aglycol component, and 0 to 5.0 mole percent of a polyfunctionalbranching agent. Said polyesters which incorporatebis(2-hydroxyethyl)isosorbide of the present invention are found to havea greater monomer incorporation rate than the isosorbide polyesters ofthe art.

[0009] A further aspect of the present invention includes polyurethaneswhich incorporate bis(2-hydroxyethyl)isosorbide. Said polyurethaneswhich incorporate bis(2-hydroxyethyl)isosorbide are comprisedessentially of 45.0 to 50.0 mole percent of a polyisocyanate component,50.0 to 0.1 mole percent of bis(2-hydroxyethyl)isosorbide and/or apolyester polyol which contains bis(2-hydroxyethyl)isosorbide, and 0 to49.9 mole percent of a glycol component.

[0010] A further aspect of the present invention includes shapedarticles produced from polymeric materials which incorporatebis(2-hydroxyethyl)isosorbide. Said polymeric materials whichincorporate bis(2-hydroxyethyl)isosorbide may be selected from the groupconsisting of polyesters, polyamide esters, polyurethanes, polyethersulfones, polyether ketones, polycarbonates, and polycarbonate esters.Said shaped articles produced from the polymeric materials whichincorporate bis(2-hydroxyethyl)isosorbide of the present invention mayinclude film, sheets, fiber, melt blown containers, molded parts, suchas cutlery, foamed parts, polymeric melt extrusion coatings ontosubstrates, polymeric solution coatings onto substrates and the like.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Preparation of bis(2-hydroxyethyl)Isosorbide:

[0012] The bis(2-hydroxyethyl)isosorbide of the present invention may bereadily prepared from isosorbide, which is derived from renewableresources, such as sugars and starches, as described above. For example,isosorbide may be modified with ethylene oxide, ethylene carbonate andthe like, to produce bis(2-hydroxyethyl)isosorbide.

[0013] The conversion of alcohols to 2-hydroxyethyl ethers is knownwithin the art. Any known method in the art may be used to convertisosorbide to bis(2-hydroxyethyl)isosorbide.

[0014] Ethylene Oxide:

[0015] For example, ethylene oxide has been used in the production of2-hydroxyethyl ethers from alcohols. Typically such a process isperformed by heating the ethylene oxide, the alcohol and a catalystsystem together, followed by recovery and purification of the resultant2-hydroxyethyl ether product. The reaction may be performed with aninert solvent. Catalyst systems which have found use in such processesinclude; acids, bases, ammonia, urea, alkali metal hydroxides, alkalimetal phenates, potassium hydroxide, alkali metal bases, organoaluminumzinc compounds, nitrogen containing catalysts, calcium acetates,strontium acetates, barium acetates, aluminum trifluoride, trialkylaluminum, mixtures of boron trifluoride and trialkyl phosphoriccompounds, zinc dialkyl materials, mixtures of boron trifluoride withmetal alkyls or metal alkoxides, mixtures of silicon tetrafluoride withmetal alkyls or metal alkoxides, mixtures of an alkali metal borohydrideand an alkali metal hydroxide. Representative art which describes thepreparation of 2-hydroxyethyl ethers from alcohols would include; U.S.Pat. Nos. 2,716,137, 2,852,566, 2,879,220, 3,350,462, 3,354,227,3,364,267, 3,395,185, 3,525,773, 3,597,502, 3,642,911, 3,644,534,3,682,849, 3,719,636, 3,910,878, 3,969,417, 4,098,818, 4,210,764,4,223,164, 4,239,917, 4,254,287, 4,282,387, 4,302,613, 4,306,093,4,453,022, 4,453,023, 4,483,941, 4,533,759, 4,754,075, 4,775,653,4,820,673, 4,886,917, 4,892,977, 4,902,658, 5,608,116 British Patent No.1,399,966, British Patent No. 1,462,133, British Patent No. 1,462,134,European Patent Application No. A0095562, European Patent ApplicationNo. 339426, French Patent No. 1,365,945, German Patent No. 2406293,Japanese Patent No. 50017976, Japanese Patent No. 50000654, JapanesePatent No. 49033183, Japanese Patent No. 62289537, Japanese Patent No.52003923, Japanese Patent No. 52051307, Japanese Patent No. 51059809 andreferences cited therein. These preparative references and thereferences cited therein are herein incorporated by reference into thepresent invention.

[0016] Catalysts that may be used with the ethylene oxide include acids,bases, ammonia, urea, alkali metal hydroxides, alkali metal phenates,potassium hydroxide, alkali metal bases, organoaluminum zinc compounds,nitrogen containing catalysts, calcium acetates, strontium acetates,barium acetates, aluminum trifluoride, trialkyl aluminum, mixtures ofboron trifluoride and trialkyl phosphoric compounds, zinc dialkylmaterials, mixtures of boron trifluoride with metal alkyls or metalalkoxides, mixtures of silicon tetrafluoride with metal alkyls or metalalkoxides, mixtures of an alkali metal borohydride and an alkali metalhydroxide, and the like and mixtures thereof. These are generally knownin the art and a skilled practitioner may readily select the specificcatalyst or combination or sequence of catalysts used. The preferredcatalyst and preferred conditions differ depending on, for example, thetype and scale of reactor to be used.

[0017] Ethylene carbonate:

[0018] Ethylene carbonate has been used in the conversion of alcohols to2-hydroxyethyl ethers. Typically this operation is performed by heatingthe alcohol, ethylene carbonate and certain catalyst systems together,followed by recovery of the resultant 2-hydroxyethyl ether product. Theprocess may be carried out with an inert solvent. Generally, thecatalyst systems may be composed of acids, bases, alkali salts ofphenols, phosphonium materials, potassium carbonate, alkali metalhydrides, alkali metal hydroxides, inorganic halide salts,triorganophosphine compounds, potassium iodide, imidazole, sodiumstannate, potassium fluoride, mixed metal oxide. Representative artwould include U.S. Pat. Nos. 2,448,767, 2,967,892, 2,987,555, 3,283,030,3,967,892, 4,261,922, 4,310,706, 4,310,707, 4,310,708, 4,341,905,5,059,723, 5,104,987, 5,157,159, 5,679,871, 5,998,568, Japanese PatentNo. 03052838, Japanese Patent No. 50004012 and references cited therein.Dow Chemical U.S.A., Experimental Ethylene carbonate XAS-1666.00LProduct Bulletin (1982), pp. 4-9, discloses hydroxyethylation reactionsin which ethylene carbonate reacts with compounds containing activehydrogen, such as alcohols, to give hydroxyethyl derivatives. Thereactions are carried out at temperatures between 100° C. to 200° C. inthe presence of metal salts such as potassium carbonate. Carbon dioxideis the principle byproduct. It is stated that ethylene carbonate yields,in most cases, the mono-ethylene oxide insertion product. TexacoChemical Company, TEXACAR.RTM. Ethylene and Propylene Carbonates ProductBulletin (1987), pp. 23-24, describes hydroxyalkylation reactions inwhich ethylene carbonate react with compounds which contain an activehydrogen, such as alcohols, to give the corresponding hydroxyethylderivatives. The reactions are run between 100 and 200° C. employing abasic catalyst, such as potassium carbonate at a 0.5 weight percentlevel. These preparative references and the references cited therein arehereby incorporated by reference into the present invention.

[0019] Catalysts that may be used with the ethylene carbonate include,for example, acids, bases, alkali salts of phenols, phosphoniummaterials, potassium carbonate, alkali metal hydrides, alkali metalhydroxides, inorganic halide salts, triorganophosphine compounds,potassium iodide, imidazole, sodium stannate, potassium fluoride, mixedmetal oxide, and the like and mixtures thereof. These are generallyknown in the art and a skilled practitioner may readily select thespecific catalyst or combination or sequence of catalysts used. Thepreferred catalyst and preferred conditions differ depending on, forexample, the type and scale of reactor to be used.

[0020] Chemical Modification:

[0021] In the chemical modification process, the isosorbide and theethylene oxide or the ethylene carbonate are combined and are heatedgradually with mixing with a catalyst or a catalyst mixture to atemperature in the range of 50 to about 300° C., preferably between 75and 200° C. Typically a stoichiometric excess of ethylene carbonate willbe employed. Optionally, a solvent inert under the reaction conditions,such as a hydrocarbon, may be employed. The exact conditions andcatalysts used will depend on the exact nature of the reactor to beemployed. The catalyst may be included initially with the reactantsand/or may be added one or more times to the mixture as it is heated.The catalyst used may be modified as the reaction proceeds. The heatingand stirring are continued for a sufficient time and a sufficienttemperature to yield a significant conversion of isosorbide tobis(hydroxyethyl)isosorbide.

[0022] Purification of bis(2-hydroxyethyl)Isosorbide:

[0023] The resulting bis(2-hydroxyethyl)isosorbide product may bepurified by any method known within the art, for example, bydistillation. As is known within the art, hydroxyethylation processeswith ethylene oxide or ethylene carbonate generally lead to a mixture ofproducts. Said mixture typically is the result of the initially formedbis(2-hydroxyethyl)isosorbide product further reacting with additionalethylene carbonate to form higher hydroxy terminated polyethers.Formation of such higher polyethers may be controlled by the amount ofadded ethylene carbonate, the exact nature of the catalyst system, andthe reaction conditions. While it is most preferred that thebis(2-hydroxyethyl)isosorbide to be used in the preparation of thepolymeric materials described below be essentially pure, it iscontemplated that bis(2-hydroxyethyl)isosorbide may include said higherhydroxy terminated polyethers derived from additional hydroxyethylationreactions between ethylene carbonate and the as formed products. It ispreferred that such impurities be below 10 weight percent of thebis(2-hydroxyethyl)isosorbide product.

[0024] A wide variety of other preparative methods for the preparationof 2-hydroxyethyl ethers have been reported within the art. For example,Shibatani, et. al., in Japanese Patent 53098917, describe the conversionof alcohols to 2-hydroxyethyl ethers by reacting the alcohols withformaldehyde, hydrogen, and carbon monoxide in the presence of oxocatalysts. Any known preparative method to produce 2-hydroxyethyl ethersmay find use in the present invention. Uses ofbis(2-hydroxyethyl)isosorbide:

[0025] Uses of bis(2-hydroxyethyl)Isosorbide:

[0026] Bis(2-hydroxyethyl)isosorbide will find many valuable uses in theart. Bis(2-hydroxyethyl)isosorbide may be chemically modified to form,for example bisacrylate esters or bis vinyl ethers, which will find usein photochemical or thermal cured vinyl resin compositions.Alternatively, bis(2-hydroxyethyl)isosorbide may be reacted withepichlorohydrin and base to form bis(glycidyl ether) adducts which mayserve in epoxy resins. For example, bis(2-hydroxyethyl)isosorbide willfind use as a monomer in polymeric compositions, such as polyesters,polyamide esters, polycarbonates, polycarbonate esters, polyurethanes,polyether sulfones, polyether ketones, polyether ether ketones, and thelike.

[0027] Polyesters:

[0028] One further aspect of the present invention includes polyesterswhich incorporate bis(2-hydroxyethyl)isosorbide. Said polyesters withbis(2-hydroxyethyl)isosorbide comonomer are comprised essentially of:

[0029] (a) 45.0 to 50.0 mole percent of a dicarboxylic acid component,

[0030] (b) 50.0 to 0.1 mole percent of bis(2-hydroxyethyl)isosorbide,

[0031] (c) 0 to 49.9 mole percent of at least one additional glycolcomponent, and

[0032] (d) 0 to 5.0 mole percent of at least one polyfunctionalbranching agent.

[0033] Said dicarboxylic acid component is meant to includeunsubstituted and substituted aromatic, aliphatic, unsaturated, andacyclic dicarboxylic acids and the lower alkyl esters of aromatic,aliphatic, unsaturated, and acyclic dicarboxylic acids having from 8carbons to 36 carbons. Specific examples of the desirable dicarboxylicacid component include terephthalic acid, dimethyl terephthalate,isophthalic acid, dimethyl isophthalate, 2,6-napthalene dicarboxylicacid, dimethyl-2,6-naphthalate, 2,7-naphthalenedicarboxylic acid,dimethyl-2,7-naphthalate, 3,4′-diphenyl ether dicarboxylic acid,dimethyl-3,4′diphenyl ether dicarboxylate, 4,4′-diphenyl etherdicarboxylic acid, dimethyl-4,4′-diphenyl ether dicarboxylate,3,4′-diphenyl sulfide dicarboxylic acid, dimethyl-3,4′-diphenyl sulfidedicarboxylate, 4,4′-diphenyl sulfide dicarboxylic acid,dimethyl-4,4′-diphenyl sulfide dicarboxylate, 3,4′-diphenyl sulfonedicarboxylic acid, dimethyl-3,4′-diphenyl sulfone dicarboxylate,4,4′-diphenyl sulfone dicarboxylic acid, dimethyl-4,4′-diphenyl sulfonedicarboxylate, 3,4′-benzophenonedicarboxylic acid,dimethyl-3,4′-benzophenonedicarboxylate, 4,4′-benzophenonedicarboxylicacid, dimethyl-4,4′-benzophenonedicarboxylate, 1,4-naphthalenedicarboxylic acid, dimethyl-1,4-naphthalate, 4,4′-methylene bis(benzoicacid), dimethyl-4,4′-methylenebis(benzoate), and the like and mixturesderived therefrom. Preferably, the aromatic dicarboxylic acid componentis derived from terephthalic acid, dimethyl terephthalate, isophthalicacid, dimethyl isophthalate, 2,6-naphthalene dicarboxylic acid,dimethyl-2,6-naphthalate, metal salts of 5-sulfo-dimethylisophthalate,oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinicacid, dimethyl succinate, methylsuccinic acid, glutaric acid, dimethylglutarate, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid,dimethyl adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioicacid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate,sebacic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylicacid, undecanedioic acid, 1,12-dodecanedicarboxylic acid,hexadecanedioic acid, docosanedioic acid, tetracosanedioic acid, dimeracid, 1,4-cyclohexanedicarboxylic acid, dimethyl-1,4-cyclohexanedicarboxylate, 1,3-cyclohexanedicarboxylic acid,dimethyl-1,3-cyclohexanedicarboxylate, 1,1-cyclohexanediacetic acid,fumaric acid, maleic anhydride, maleic acid, hexahydrophthalic acid,phthalic acid, and the like and mixtures derived therefrom. Theseexamples should not be considered limiting. Essentially any dicarboxylicacid known within the art may find utility within the present invention.

[0034] Said other glycol component is meant to include unsubstituted,substituted, straight chain, branched, cyclic aliphatic,aliphatic-aromatic or aromatic diols having from 2 carbon atoms to 36carbon atoms and poly(alkylene ether) glycols with molecular weightsbetween about 250 to 4,000. Specific examples of the desirable otherglycol component include ethylene glycol, 1,3-propanediol,1,2-propanediol, 1,2-butanediol, 1,3-butanediol,1,3-2-methylpropanediol, neopentyl glycol, 1,4-butanediol,1,3-hexanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol,1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,1,14-tetradecanediol, 1,16-hexadecanediol, dimer diol,4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane,1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene glycol),poly(ethylene ether) glycols, poly(butylene ether) glycols and the likeand mixtures derived therefrom. These examples should not be interpretedas limiting. Essentially any other glycol known within the art may finduse within the present invention.

[0035] Said optional polyfunctional branching agent is meant to includeany material with three or more carboxylic acid functions, hydroxyfunctions or a mixture thereof. Specific examples of the desirablepolyfunctional branching agent component include1,2,4-benzenetricarboxylic acid, (trimellitic acid),trimethyl-1,2,4-benzenetricarboxylate, 1,2,4-benzenetricarboxylic anhydride, (trimellitic anhydride), 1,3,5-benzenetricarboxylic acid,1,2,4,5-benzenetetracarboxylic acid, (pyromellitic acid),1,2,4,5-benzenetetracarboxylic dianhydride, (pyromellitic anhydride),3,3′,4,4′-benzophenonetetracarboxylic dianhydride,1,4,5,8-naphthalenetetracarboxylic dianhydride, citric acid,tetrahydrofuran-2,3,4,5-tetracarboxylic acid,1,3,5-cyclohexanetricarboxylic acid, pentaerythritol,2-(hydroxymethyl)-1,3-propanediol, 2,2-bis(hydroxymethyl)propionic acid,trimer acid, and the like and mixtures therefrom. This should not beconsidered limiting. Essentially any polyfunctional material whichincludes three or more carboxylic acid or hydroxyl functions may finduse within the present invention. Said polyfunctional branching agentmay be included when higher resin melt viscosity is desired for specificend uses. Examples of said end uses may include melt extrusion coatings,melt blown films or containers, foam and the like.

[0036] To give the desired physical properties for many end uses, thepolyesters which incorporate bis(2-hydroxyethyl)isosorbide of thepresent invention need to have an inherent viscosity, which is anindicator of molecular weight, of at least equal to or greater than0.15. More desirably, the inherent viscosity, (IV), of polyesters whichinclude bis(2-hydroxyethyl)isosorbide will be at least equal to 0.35dL/g, as measured on a 0.5 percent (weight/volume) solution of thecopolyester in a 50:50 (weight) solution of trifluoroaceticacid:dichloromethane solvent system at room temperature. These inherentviscosities will be sufficient for some applications. Higher inherentviscosities are desirable for many other applications, such as films,bottles, sheet, molding resin and the like. The polymerizationconditions may be adjusted to obtain the desired inherent viscosities upto at least about 0.5 and desirably higher than 0.65 dL/g. Furtherprocessing of the polyester may achieve inherent viscosities of 0.7,0.8, 0.9, 1.0, 1.5, 2.0 dL/g and even higher.

[0037] The molecular weight is normally not measured directly. Instead,the inherent viscosity of the polymer in solution or the melt viscosityis used as an indicator of molecular weight. The inherent viscositiesare an indicator of molecular weight for comparisons of samples within apolymer family, such as poly(ethylene terephthalate), poly(butyleneterephthalate), etc., and are used as the indicator of molecular weightherein.

[0038] Alternatively, certain polyester end uses prefer relatively lowmolecular weight materials. For example, polyester polyols are used inthe preparation of, for example, polyurethanes and polycarbonate esters.The polyester polyols of the present invention which incorporatebis(2-hydroxyethyl)isosorbide may have molecular weights in the rangebetween 500 and 10,000.

[0039] The polyesters of the present invention may be prepared byconventional polycondensation techniques. A review reference onpolyesters and their manufacture is Anthony J. East, Michael Golden, andSubhash Makhija, in Encyclopedia of Chemical Technology, vol. 19, fourthedition, Executive Editor, Jacqueline I. Kroschwitz, Editor, MaryHowe-Grant, pp. 609-653 (1996), which is hereby incorporated byreference in the present invention. The product compositions may varysomewhat based on the method of preparation used, particularly in theamount of diol that is present within the polymer. These methods includethe reaction of the diol monomers with the acid chlorides. For example,acid chlorides of the dicarboxylic acid component may be combined withthe bis(2-hydroxyethyl)isosorbide and the other glycol component in asolvent, such as toluene, in the presence of a base, such as pyridine,which neutralizes the hydrochloric acid as it is produced. Suchprocedures are known. See, for example, R. Storbeck, et. al., in J.Appl. Polymer Science, Vol. 59, pp. 1199-1202 (1996). Other well knownvariations using acids chlorides may also be used, such as theinterfacial polymerization method, or the monomers may simply be stirredtogether while heating.

[0040] When an isosorbide-containing polyester is made using acidchlorides, the ratio of the monomer units in the product polymer isabout the same as the ratio of reacting monomers. Therefore, the ratioof monomers charged to the reactor is about the same as the desiredratio in the product. A stoichiometric equivalent of the diol componentsand the diacid components generally will be used to obtain a highmolecular weight polymer.

[0041] Polyester Preparation:

[0042] Preferably, the polyesters which incorporatebis(2-hydroxyethyl)isosorbide of the present invention will be producedthrough a melt polymerization method. In the melt polymerization method,the dicarboxylic acid component, (either as acids, esters, or mixturesthereof), the bis(2-hydroxyethyl)isosorbide, the other glycol componentand optionally the polyfunctional branching agent, are combined in thepresence of a catalyst to a high enough temperature that the monomerscombine to form esters and diesters, then oligomers, and finallypolymers. The polymeric product at the end of the polymerization processis a molten product. Generally, the other diol component is volatile anddistills from the reactor as the polymerization proceeds. Suchprocedures are known. See, for example, U.S. Pat. Nos. 3,563,942,3,948,859, 4,094,721, 4,104,262, 4,166,895, 4,252,940, 4,390,687,4,419,507, 4,585,687, 5,053,482, 5,292,783, 5,446,079, 5,480,962, and6,063,464 and the references cited therein, which are hereinincorporated by reference.

[0043] The melt process conditions of the present invention,particularly the amounts of monomers used, depend on the polymercomposition that is desired. The amount ofbis(2-hydroxyethyl)isosorbide, other glycol component, dicarboxylic acidcomponent, and branching agent are desirably chosen so that the finalpolymeric product contains the desired amounts of the various monomerunits, desirably with equimolar amounts of monomer units derived fromthe respective diol and diacid components. Because of the volatility ofsome of the monomers, especially some of the other glycol components,and depending on such variables as whether the reactor is sealed, (i.e.,is under pressure), the polymerization temperature ramp rate, and theefficiency of the distillation columns used in synthesizing the polymer,some of the monomers may need to be included in excess at the beginningof the polymerization reaction and removed by distillation as thereaction proceeds. This is particularly true of the other glycolcomponent.

[0044] The exact amount of monomers to be charged to a particularreactor is readily determined by a skilled practitioner, but often willbe in the ranges below. Excesses of the diacid, diol, andbis(2-hydroxyethyl)isosorbide are often desirably charged, and theexcess diacid, diol and bis(2-hydroxyethyl)isosorbide is desirablyremoved by distillation or other means of evaporation as thepolymerization reaction proceeds. The other glycol component isdesirably charged at a level 0 to 100 percent greater than the desiredincorporation level in the final product. For examples of the otherglycol component which are volatile under the polymerization conditions,such as ethylene glycol, 1,3-propanediol, or 1,4-butanediol, 30 to 100percent excesses are desirably charged. For less volatile examples ofthe other glycol component, such as dimer diol, no excesses need bedesirably charged.

[0045] The amount of monomers varies widely because of the widevariation in the monomer loss during polymerization, depending on theefficiency of distillation columns and other kinds of recovery andrecycle systems and the like, and are only an approximation. Exactamounts of monomers that are charged to a specific reactor to achieve aspecific composition are readily determined by a skilled practitioner.

[0046] In the polymerization process, the monomers are combined, and areheated gradually with mixing with a catalyst or catalyst mixture to atemperature in the range of 200° C. to about 300° C., desirably 250° C.to 295° C. The exact conditions and the catalysts depend on whether thediacids are polymerized as true acids or as dimethyl esters. Thecatalyst may be included initially with the reactants, and/or may beadded one or more times to the mixture as it is heated. The catalystused may be modified as the reaction proceeds. The heating and stirringare continued for a sufficient time and to a sufficient temperature,generally with removal by distillation of excess reactants, to yield amolten polymer having a high enough molecular weight to be suitable formaking fabricated products.

[0047] Catalysts that may be used include salts of Li, Ca, Mg, Mn, Zn,Pb, Sb, Sn, Ge, and Ti, such as acetate salts and oxides, includingglycol adducts, and Ti alkoxides. These catalysts are generally known inthe art, and a skilled practitioner may readily select the specificcatalyst or combination or sequence of catalysts used. The preferredcatalyst and preferred conditions differ depending on, for example,whether the diacid monomer is polymerized as the free diacid or as adimethyl ester and the exact chemical identity of the other glycolcomponent.

[0048] The monomer composition of the polymer is chosen for specificuses and for specific sets of properties. For uses where a partiallycrystalline polymer is desired, as for example food and beveragecontainers, specifically, such as hot fill or cold fill bottles, fibers,and films, the polymer will generally have a monomer composition whichallows for some crystallinity in the final polymer product.

[0049] For applications where it is desirable to have an amorphouspolymer, for example, transparent optical articles or solvent solublecopolyesters, the amount of bis(2-hydroxyethyl)isosorbide moiety isgenerally greater than 2.0 mole percent. As one skilled in the art willappreciate, the exact thermal properties observed will be a complexfunction of the exact chemical identity and level of each componentutilized in the copolyester composition.

[0050] Polymers can be made by the melt condensation process abovehaving adequate inherent viscosity for many applications. Solid statepolymerization may be used to achieve even higher inherent viscosities(molecular weights).

[0051] Crystallinity:

[0052] The product made by melt polymerization, after extruding, coolingand pelletizing, may be essentially noncrystalline. Noncrystallinematerial can be made semicrystalline by heating it to a temperatureabove the glass transition temperature for an extended period of time.This induces crystallization so that the product can then be heated to ahigher temperature to raise the molecular weight.

[0053] The polymer may also be crystallized prior to solid statepolymerization by treatment with a relatively poor solvent forpolyesters which induces crystallization. Such solvents reduce the glasstransition temperature (Tg) allowing for crystallization. Solventinduced crystallization is known for polyesters and is described in U.S.Pat. Nos. 5,164,478 and 3,684,766, which are incorporated herein byreference.

[0054] The semicrystalline polymer is subjected to solid statepolymerization by placing the pelletized or pulverized polymer into astream of an inert gas, usually nitrogen, or under a vacuum of 1 Torr,at an elevated temperature, but below the melting temperature of thepolymer for an extended period of time.

[0055] Some of the above described polyesters which incorporatebis(2-hydroxyethyl)isosorbide are found to be t soluble in common,non-halogenated, polar solvents. Examples of said non-halogenated, polarsolvents include tetrahydrofuran, dimethyl acetamide, dimethylformamide, N-methylpyrollidone, dimethylsulfoxide, and the like.Tetrahydrofuran is preferred. Certain examples of the polyesters whichincorporate bis(2-hydroxyethyl)isosorbide of the current invention arefound to be readily soluble in said solvents and the resulting polymersolutions are found to provide clear films.

[0056] Additives:

[0057] It is understood that the polyesters which incorporatebis(2-hydroxyethyl)isosorbide of the present invention may be used withadditives known within the art. Such additives may include thermalstabilizers, for example, phenolic antioxidants, secondary thermalstabilizers, for example, thioethers and phosphites, UV absorbers, forexample benzophenone- and benzotriazole-derivatives, UV stabilizers, forexample, hindered amine light stabilizers, (HALS), and the like. Saidadditives may further include plasticizers, processing aides, flowenhancing additives, lubricants, pigments, flame retardants, impactmodifiers, nucleating agents to increase crystallinity, antiblockingagents such as silica and the like. In addition, the compositions of thepresent invention may be filled with, for example, wood flour, gypsum,wollastonite, chalk, kaolin, clay, silicon oxide, calcium terephthalate,aluminum oxide, titanium oxide, calcium phosphate, lithium fluoride,cellulose, starch, chemically modified starch, thermoplastic starch,calcium carbonate, reinforcing agents, such as glass, and the like. Thecompositions of the present invention may also find use as a componentof a polymer blend with other polymers, such as cellulose ethers,thermoplastic starch, poly(vinyl alcohol), other polyesters,polycarbonates, nylons, polyamides, polyolefins, polyolefin elastomers,and the like. This should not be considered limiting. Essentially anyadditive and filler of the art may find use in the polyesters whichincorporate bis(2-hydroxyethyl)isosorbide of the present invention.

[0058] Biodegradability:

[0059] Some of the polyester compositions of the present invention whichincorporate bis(2-hydroxyethyl)isosorbide will be found to bebiodegradable, as determined through the below mentioned ISO 14855composting method. Preferably, said biodegradable copolyester of thepresent invention which incorporate bis(2-hydroxyethyl)isosorbide willcontain, at least as a portion of the dicarboxylic acid component,aliphatic dicarboxylic acids.

[0060] The inadequate treatment of municipal solid waste which is beingput in landfills and the increasing addition of nondegradable materials,including plastics, to municipal solid waste streams are combining todrastically reduce the number of landfills available and to increase thecosts of municipal solid waste disposal. While recycling of reusablecomponents of the waste stream is desirable in many instances, the costsof recycling and the infrastructure required to recycle materials issometimes prohibitive. In addition, there are some products which do noteasily fit into the framework of recycling. The composting ofnon-recyclable solid waste is a recognized and growing method to reducesolid waste volume for landfilling and/or making a useful product fromthe waste to improve the fertility of fields and gardens. One of thelimitations to marketing such compost is the visible contamination byundegraded plastic, such as film or fiber fragments.

[0061] It is desired to provide components which are useful indisposable products and which are degraded into less contaminating formsunder the conditions typically existing in waste composting processes.These conditions may involve temperatures no higher than 70 degrees C.,and averaging in the 55-60 degrees C. range, humid conditions as high as100 percent relative humidity, and exposure times which range from weeksto months. It is further desirable to provide disposable componentswhich will not only degrade aerobically/anaerobically in composting, butwill continue to degrade in the soil or landfill. As long as water ispresent, they will continue to break down into low molecular weightfragments which can be ultimately biodegraded by microorganismscompletely into biogas, biomass, and liquid leachate, as for naturalorganics like wood.

[0062] Polyesters have been considered for biodegradable articles andend uses in the past. Said biodegradable polyesters can be described asbelonging to three general classes; aliphatic polyesters,aliphatic-aromatic polyesters and sulfonated aliphatic-aromaticpolyesters.

[0063] Aliphatic polyesters are meant to include polyesters derivedsolely from aliphatic dicarboxylic acids, such as poly(ethylenesuccinate), poly(1,4-butylene adipate), and the like, as well aspoly(hydroxyalkanates), such as polyhydroxybutyrate, polylactide,polycaprolactone, polyglycolide and the like. Representative art in thearea of aliphatic polyesters includes, for example; Clendinning, et.al., in U.S. Pat. No. 3,932,319, Casey, et. al., in U.S. Pat. No.4,076,798, Tokiwa, et. al., in U.S. Pat. No. 5,256,711, Buchanan, et.al., in U.S. Pat. Nos. 5,292,783, 5,559,171, 5,580,911, and 5,599,858,Tajima, et. al., in U.S. Pat. No. 5,300,572, Taka, et. al., in U.S. Pat.No. 5,324,794, Takahashi, in U.S. Pat. No. 5,349,028, Imaizumi, in U.S.Pat. No. 5,530,058, Itoh, et. al., in U.S. Pat. No. 5,391,700 and U.S.Pat. No. 5,616,681, Noda, et. al., in U.S. Pat. Nos. 5,653,930 and5,780,368, Imaizumi, et. al., in U.S. Pat. No. 5,714,569, Kuroda, et.al., in U.S. Pat. No. 5,786,408, and Sugimoto, in U.S. Pat. No.6,083,621.

[0064] Aliphatic-aromatic polyesters are meant to include polyestersderived from a mixture of aliphatic dicarboxylic acids and aromaticdicarboxylic acids. Representative teachings in the area ofaliphatic-aromatic copolyesters include, for example; Sublett, et. al.,in U.S. Pat. No. 3,948,859, Buxbaum, et. al., in U.S. Pat. No.4,166,895, Horlbeck, et. al., in U.S. Pat. No. 4,328,059, Sublett, inU.S. Pat. No. 4,419,507, Buchanan, et. al., in U.S. Pat. No. 5,446,079,Gordon, et. al., in U.S. Pat. No. 5,594,076, Khemani, in U.S. Pat. Nos.5,661,193 and 6,020,393, and Lorcks, et. al., in U.S. Pat. No.6,096,809.

[0065] Sulfonated aliphatic-aromatic polyesters are meant to includepolyesters derived from a mixture of aliphatic dicarboxylic acids andaromatic dicarboxylic acids and, in addition, incorporate a sulfonatedmonomer, such as the metal salts of 5-sulfoisophthalic acid.Representative art teachings in the area of sulfonatedaliphatic-aromatic copolyesters includes, for example; King, et. al., inU.S. Pat. No. 3,936,389, Griffing, et. al., in U.S. Pat. No. 3,018,272,Kotera, et. al., in U.S. Pat. No. 4,340,519, Tung, in U.S. Pat. No.4,390,687, Miller, in U.S. Pat. No. 4,394,442, Posey, et. al., in U.S.Pat. Nos. 4,476,189, 4,525,419, and 4,585,687, Tietz, in U.S. Pat. No.5,053,482, Tietz, in U.S. Pat. No. 5,097,005, Gallagher, et. al., inU.S. Pat. No. 5,097,004, Gallagher, et. al., in U.S. Pat. No. 5,171,308,Romesser, et. al., in U.S. Pat. No. 5,295,985, Gallagher, et. al., inU.S. Pat. No. 5,171,309, Gallagher, et. al., in U.S. Pat. No. 5,219,646,Fish, et. al., in U.S. Pat. No. 5,354,616, Warzelhan, et. al., in U.S.Pat. Nos. 5,817,721, 5,880,220, 5,889,135, and 6,018,004, and Yamamoto,et. al., in U.S. Pat. No. 6,103,858.

[0066] Other Polyester Embodiments:

[0067] Unsaturated polyesters are also known within the art. Referenceis made to Jeffrey Selley in Encyclopedia of Chemical Technology, vol.19. Fourth ed., Executive Editor, Jacqueline I. Kroschwitz, Editor, MaryHowe-Grant, pp. 654-678 (1996). Unsaturated polyesters which incorporatebis(2-hydroxyethyl)isosorbide of the present invention may be preparedas described therein.

[0068] Polyester polyols are known within the art. They are used, forexample, in the preparation of coatings, paints and polyurethanes.Polyester polyols which incorporate bis(2-hydroyethyl)isosorbide of thepresent invention may be produced by any known method in the art.Generally this includes adding a dicarboxylic acid component, abis(2-hydroxyethyl) isosorbide component, an other glycol component andoptionally a catalyst and a branching agent together, typicallyutilizing a molar excess of the glycol component, (the combination ofthe bis(2-hydroxyethyl)isosorbide component and the other glycolcomponent), and heating to the desired molecular weight, typically asmeasured by the hydroxyl or acid number. The acid number is defined byDIN 53 402 and the hydroxyl number is defined by DIN 53 240. Typically,polyester polyols will preferably have molecular weights between 500 and10,000, more preferably between 500 and 5,000. However, higher molecularweight polyester polyols are producible. Representative referencesinclude U.S. Pat. Nos. 3,994,851, 4,104,240, 4,243,705, 4,540,771,4,888,441, 4,922,002, 5,976,706, 6,087,466, and 6,087,466, and thereferences cited therein. These references are hereby incorporated byreference in the present invention.

[0069] Polyester amides are known within the art. Polyester amides ofthe present invention which incorporate bis(2-hydroxyethyl)isosorbideare producible by any known methods in the art. Representativereferences include, for example, U.S. Pat. Nos. 4,709,004, 4,835,248,5,349,011, 5,457,144, and the references cited therein.

[0070] Polyurethanes:

[0071] A further aspect of the present invention includes polyurethaneswhich incorporate bis(2-hydroxyethyl)isosorbide. Said polyurethaneswhich incorporate bis(2-hydroxyethyl)isosorbide are comprisedessentially of:

[0072] (a) 45.0 to 50.0 mole percent of a polyisocyanate component,

[0073] (b) 50.0 to 0.1 mole percent of bis(2-hydroxyethyl)isosorbide,

[0074] (c) 0 to 5.0 mole percent at least one polyester polyol, and

[0075] (d) 0 to 49.9 mole percent of at least one additional glycolcomponent.

[0076] Said polyisocyanate component is meant to include bothpolyisocyanates and chemically blocked isocyanates, such as withmethanol, oximes such as methylethyl ketone oxime, lactams such ascaprolactam, imidazole or phenols. Specific examples of usefulpolyisocyanate components includes diphenylmethane diisocyanate, toluenediisocyanate, xylene diisocyanate, phenylene diisocyanate, naphthalenediisocyanate, 4,4′-methylene-bis-(cyclohexyl isocyanate), isophoronediisocyanate, 1,6-hexamethylene diisocyanate, the biuret from1,6-hexamethylene diisocyanate commercially available from MobayChemical Company as DESMODUR N, 1,12-dodecane diisocyanate and the likeand mixtures thereof.

[0077] Said other glycol component is meant to include unsubstituted,substituted, straight chain, branched, cyclic aliphatic,aliphatic-aromatic or aromatic diols having from 2 carbon atoms to 36carbon atoms and poly(alkylene ether) glycols with molecular weightsbetween about 250 to 4,000. Specific examples of the desirable otherglycol component include ethylene glycol, 1,3-propanediol,1,2-propanediol,1,2-butanediol, 1,3-butanediol, 1,3-2-methylpropanediol,neopentyl glycol, 1,4-butanediol, 1,3-hexanediol, 1,6-hexanediol,2-ethyl-2-methyl-1,3-propanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, dimerdiol, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane,1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene glycol),poly(ethylene ether) glycols, poly(butylene ether) glycols and the likeand mixtures derived therefrom. This should not be taken as limiting.Essentially any other glycol known within the art may find use withinthe present invention.

[0078] Catalysts, for example, such as organotin compounds, may beemployed in the polymerization reaction to form polyurethanes.

[0079] Methods to prepare polyurethanes are known within the art.Reference is made to a recent review by Henri Ulrich in Encyclopedia ofChemical Technology, vol. 24, fourth ed., Executive Editor, JacquelineI. Kroschwitz, Editor, Mary Howe-Grant, pp. 695-726 (1996).Polyurethanes which incorporate bis(2-hydroxyethyl)isosorbide orpolyester polyols which incorporate bis(2-hydroxyethyl)isosorbide of thepresent invention may be produced by any known method in the art.Representative art includes, for example U.S. Pat. Nos. 3,943,077,4,139,501, 4,251,635, 4,258,141, 4,284,730, 4,317,889, 4,433,071,6,087,466, 6,103,822, 6,111,048, 6,114,403, and the references citedtherein.

[0080] Polyethers:

[0081] Polyethers, including polyether sulfones and polyether ketones,are known within the art. The polyethers of the present invention, whichincludes polyether sulfones and polyether ketones which incorporatebis(2-hydroxyethyl)isosorbide, are producible by any known method in theart. Reference is made to Dwain M. White in Encyclopedia for ChemicalTechnology, vol. 19, fourth editions, Executive Editor, Jacqueline I.Kroschwitz, Editor, Mary Howe-Grant, pp. 678-701 (1996) and thereferences cited therein.

[0082] Polycarbonates:

[0083] Polycarbonates and polycarbonate esters are known within the art.The polycarbonates and polycarbonate esters which incorporatebis(2-hydroxyethyl)isosorbide and polyester polyols which incorporatebis(2-hydroxyethyl)isosorbide of the present invention are producible byany known method of the art. Reference is made to Daniel J. Brunelle inEncyclopedia of Chemical Technology, volume 19, fourth edition,Executive Editor, Jacqueline I. Kroschwitz, Editor, Mary Howe-Grant, pp.584-608 (1996) and the references cited therein. Further art referencesinclude, for example, U.S. Pat. Nos. 4,041,018, 4,104,217, 4,267,120,and the references cited therein.

[0084] Shaped Articles:

[0085] As a further aspect of the present invention, the polymericmaterials which incorporate bis(2-hydroxyethyl)isosorbide of the presentinvention have been found to be useful within a wide variety of shapedarticles. Said polymeric materials of the present invention whichincorporate bis(2-hydroxyethyl)isosorbide and/or polyester polyols whichincorporate bis(2-hydroxyethyl)isosorbide may include, for example,polyesters, polyamide esters, polyurethanes, polycarbonates,polycarbonate esters, polyether sulfones, polyether ketones and thelike. Examples of shaped articles include film, sheets, fiber, meltblown containers, molded parts, such as cutlery, foamed parts, polymericmelt extrusion coatings onto substrates, polymeric solution coatingsonto substrates and the like. The polymeric materials which incorporatebis(2-hydroxyethyl)isosorbide of the present invention may be solutionor melt processed to form coatings, films and the like. Coatings may beproduced by coating a substrate with polymer solutions of the polymericmaterials of the present invention followed by drying, by coextrudingthe polymeric materials of the present invention with other materials,or by melt coating a preformed substrate with the polymeric materials ofthe present invention. This should not be considered limiting. Thepolymeric materials of the present invention will find utility inessentially any process known within the art. Said coatings derived fromthe polymeric materials of the present invention will find utility asbarriers to moisture, oxygen, carbon dioxide and the like. Said coatingsderived from the polymeric materials of the present invention will alsobe useful as adhesives. Films of the polymeric materials of the presentinvention may be produced by any known art method, including, forexample, solution or melt casting.

[0086] Films and Sheets:

[0087] A further specific aspect of the present invention includesshaped articles in the form of films produced from polymeric materialswhich incorporate bis(2-hydroxyethyl)isosorbide. Said films and sheetsof the present invention which incorporate bis(2-hydroxyethyl)isosorbideand/or polyester polyols which incorporate bis(2-hydroxyethyl)isosorbidemay include, for example, polyesters, polyamide esters, polyurethanes,polycarbonates, polycarbonate esters, polyether sulfones, polyetherketones and the like.

[0088] Film Applications:

[0089] Polymeric films have a variety of uses, such as in packaging,especially of foodstuffs, adhesives tapes, insulators, capacitors,photographic development, x-ray development and as laminates, forexample. For many of these uses, the heat resistance of the film is animportant factor. Therefore, a higher melting point and glass transitiontemperature are desirable to provide better heat resistance and morestable electrical characteristics. Further, it is desired that thesefilms have good tensile strength and a high elongation at break.

[0090] The polymeric materials which incorporatebis(2-hydroxyethyl)isosorbide of the present invention may be formedinto a film for use in any one of the many different applications, suchas food packaging, labels, dielectric insulation, a water vapor barrieror the like. The monomer composition of the polymeric material ispreferably chosen to result in a partially crystalline polymer desirablefor the formation of film, wherein the crystallinity provides strengthand elasticity. As first produced, the polymeric material is generallysemi-crystalline in structure. The crystallinity increases on reheatingand/or stretching of the polymer, as occurs in the production of film.

[0091] In the process of the invention, film is made from the polymer byany process known in the art. The difference between a film and a sheetis the thickness, but there is no set industry standard as to when afilm becomes a sheet. For purposes of this invention, a film is lessthan or equal to 0.25 mm (10 mils) thick, preferably between about 0.025mm and 0.15 mm (1 mil and 6 mils). However, thicker films can be formedup to a thickness of about 0.50 mm (20 mils).

[0092] Film Extrusion:

[0093] The film of the present invention is preferably formed by eithersolution casting or extrusion. Extrusion is particularly preferred forformation of “endless” products, such as films and sheets, which emergeas a continuous length. In extrusion, the polymeric material, whetherprovided as a molten polymer or as plastic pellets or granules, isfluidized and homogenized. This mixture is then forced through asuitably shaped die to produce the desired cross-sectional film shape.The extruding force may be exerted by a piston or ram (ram extrusion),or by a rotating screw (screw extrusion), which operates within acylinder in which the material is heated and plasticized and from whichit is then extruded through the die in a continuous flow. Single screw,twin screw, and multi-screw extruders may be used as known in the art.Different kinds of die are used to produce different products, such asblown film (formed by a blow head for blown extrusions), sheets andstrips (slot dies) and hollow and solid sections (circular dies). Inthis manner, films of different widths and thickness may be produced,and, in some cases, such as when film is used as a coating, it may beextruded directly onto the object to be coated. For example, wires andcables can be sheathed directly with polymeric films extruded fromoblique heads. As a further example, laminated paper coatings can beproduced by melt extruding the polymer directly onto paperboard. Afterextrusion, the polymeric film is taken up on rollers, cooled and takenoff by means of suitable devices which are designed to prevent anysubsequent deformation of the film.

[0094] Using extruders as known in the art, film can be produced byextruding a thin layer of polymer over chilled rolls and then furtherdrawing down the film to size by tension rolls. Preferably, the finishedfilm is less than or equal to 0.25 mm thick. Blown film, which isgenerally stronger, tougher, and made more rapidly than cast film, ismade by extruding a tube. In producing blown film, the melt flow isturned upward from the extruder and fed through an annular die. As thistube leaves the die, internal pressure is introduced through the diemandrel with air, which expands the tube from about 1.5 to about 2.5times the die diameter and simultaneously draws the film, causing areduction in thickness. The resulting sleeve is subsequently slit alongone side, making a larger film width than could be conveniently made viathe cast film method. In extrusion coating, the substrate (paper, foil,fabric, polymeric film, and the like) is compressed together with theextruded polymeric melt by means of pressure rolls so that the polymerimpregnates the substrate for maximum adhesion.

[0095] For manufacturing large quantities of film, a sheeting calenderis employed. The rough film is fed into the gap of the calender, amachine comprising a number of heatable parallel cylindrical rollerswhich rotate in opposite directions and spread out the polymer andstretch it to the required thickness. The last roller smooths the filmthus produced. If the film is required to have a textured surface, thefinal roller is provided with an appropriate embossing pattern.Alternatively, the film may be reheated and then passed through anembossing calender. The calender is followed by one or more coolingdrums. Finally, the finished film is reeled up.

[0096] Alternatively, as mentioned previously, a supporting material maybe coated directly with a film. For example, textile fabrics, paper,cardboard, metals, various building materials and the like, may becoated directly with the polymeric material for the purpose ofelectrical insulation, protection against corrosion, protection againstthe action of moisture or chemicals, impermeability to gases andliquids, or increasing the mechanical strength. One process to achievethis is referred to as melt extrusion of the polymeric melt onto asubstrate. Coatings are applied to textiles, foil, and other sheetmaterials by continuously operating spread-coating machines. A coatingknife, such as a “doctor knife”, ensures uniform spreading of thecoating materials (in the form of solution, emulsions, or dispersions inwater or an organic medium) on the supporting material, which is movedalong by rollers. The coating is then dried. Alternatively, when thecoating is applied to the supporting material in the form of a polymericfilm, the process is called laminating.

[0097] Metal articles can also be coated with the polymeric film bymeans of the whirl sintering process. The articles, heated to above themelting point of the polymer, are introduced into a fluidized bed ofpowdered polymer wherein the polymer particles are held in suspension bya rising stream of air, thus depositing a coating on the metal bysintering.

[0098] Extruded films may also be used as the starting material forother products. For example, the film may be cut into small segments foruse as feed material for other processing methods, such as injectionmolding.

[0099] A film may also be made by solution casting, which produces moreconsistently uniform gauge film than that made by melt extrusion.Solution casting comprises dissolving polymeric granules, powder or thelike in a suitable solvent with any desired formulant, such as aplasticizer or colorant. The solution is filtered to remove dirt orlarge particles and cast from a slot die onto a moving belt, preferablyof stainless steel, dried, whereon the film cools. The extrudatethickness is five to ten times that of the finished film. The film maythen be finished in a like manner to the extruded film.

[0100] One of ordinary skill in the art will be able to identifyappropriate process parameters based on the polymeric composition andprocess used for film formation.

[0101] Sheet Applications:

[0102] For purposes of this invention, a sheet is greater than about0.25 mm (10 mils) thick, preferably between about 0.25 mm and 25 mm,more preferably from about 2 mm to about 15 mm, and even more preferablyfrom about 3 mm to about 10 mm. In a preferred embodiment, the sheets ofthe present invention have a thickness sufficient to cause the sheet tobe rigid, which generally occurs at about 0.50 mm and greater. However,sheets greater than 25 mm, and thinner than 0.25 mm may be formed.

[0103] Polymeric sheets have a variety of uses, such as in signage,glazing, (such as in bus stop shelters, sky lights or recreationalvehicles), thermoforming articles, automobile lights, displays anddisplay substrates, for example. For many of these uses, the heatresistance of the sheet is an important factor. Therefore, a highermelting point and glass transition temperature are desirable to providebetter heat resistance and greater stability. Further, it is desiredthat these sheets have ultraviolet (UV) and scratch resistance, goodtensile strength, high optical clarity, and good impact strength,particularly at low temperatures.

[0104] Various polymeric compositions have been used in an attempt tomeet all of the above criteria. In particular, poly(ethyleneterephthalate) (PET) has been used to form low-cost sheets for manyyears. However, these PET sheets have poor low temperature impactstrength, a low glass transition temperature (Tg) and a high rate ofcrystallization. Thus, PET sheets cannot be used at low temperaturesbecause of the danger of breakage and they cannot be used at hightemperatures because the polymer crystallizes, thereby diminishingoptical clarity.

[0105] Polycarbonate sheets can be used in applications where lowtemperature impact strength is needed, or a high service temperature isrequired. In this regard, polycarbonate sheets have high impactstrengths at low temperatures as well as a high Tg which allows them tobe used in high temperature applications. However, polycarbonate haspoor solvent resistance, thereby limiting its use in certainapplications, and is prone to stress induced cracking. Polycarbonatesheets also provide greater impact strength than is needed for certainapplications, making them costly and inefficient for use.

[0106] Sheet Preparation:

[0107] The polymeric sheets of the present invention may be formed byany process known in the art, such as extrusion, solution casting orinjection molding. The parameters for each of these processes can beeasily determined by one of ordinary skill in the art depending uponviscosity characteristics of the copolyester and the desired thicknessof the sheet. The sheet of the present invention is preferably formed byeither solution casting or extrusion as described above for filmextrusion and film casting. Further, sheets and sheet-like articles,such as discs, may be formed by injection molding by any method known inthe art.

[0108] The sheets of the present invention as described above may bethermoformed by any known method into any desirable shape, such ascovers, skylights, shaped greenhouse glazing, displays, food trays, andthe like. The thermoforming is accomplished by heating the sheet to asufficient temperature and for sufficient time to soften the polymericmaterial of the present invention so that the sheet can be easily moldedinto the desired shape. In this regard, one of ordinary skill in the artcan easily determine the optimal thermoforming parameters depending uponthe viscosity and crystallization characteristics of the polymericsheet.

[0109] Laminate and Multilayer Applications:

[0110] The polymeric films and sheet of the invention may be combinedwith other polymeric materials during extrusion and/or finishing to formlaminates or multilayer films and sheets with improved characteristics,such as water vapor resistance. In particular, the polymeric sheet ofthe invention may be combined with one or more of the following:poly(ethylene terephthalate) (PET), aramid, polyethylene sulfide (PES),polyphenylene sulfide (PPS), polyimide (PI), polyethylene imine (PEI),poly(ethylene naphthalate) (PEN), polysulfone (PS), polyether etherketone (PEEK), olefins, polyethylene, poly(cyclic olefins), cellulose,polyamides, nylons, elastomers, poly(phenylene oxide) (PPO), andcyclohexylene dimethylene terephthalate and the like, for example. Otherpolymers may also find utility within the present invention. Amultilayer or laminate sheet may be made by any method known in the art,and may have as many as five or more separate layers joined together byheat, adhesive and/or tie layer, as known in the art.

[0111] Post-Forming Operations:

[0112] The film and sheet extrusion processes of the invention can becombined with a variety of post-extruding operations for expandedversatility. Such post-forming operations include altering round to ovalshapes, blowing the film or sheet to different dimensions, machining andpunching, biaxial stretching and the like, as known to those skilled inthe art.

[0113] Regardless of how the film or sheet is formed, it is desirablysubjected to biaxial orientation by stretching in both the machine andtransverse direction after formation. The machine direction stretch isinitiated in forming the film or sheet simply by rolling out and takingup the film or sheet. This inherently stretches the film or sheet in thedirection of take-up, orienting some of the fibers. Although thisstrengthens the film or sheet in the machine direction, it allows thefilm or sheet to tear easily in the direction at right angles becauseall of the fibers are oriented in one direction.

[0114] Therefore, biaxially stretched films and sheets are preferred forcertain uses where uniformity is desired. Biaxial stretching orients thefibers parallel to the plane of the film or sheet, but leaves the fibersrandomly oriented within the plane of the film or sheet. This providessuperior tensile strength, flexibility, toughness and shrinkability, forexample, in comparison to non-oriented films or sheets. It is desirableto stretch the film or sheet along two axes at right angles to eachother. This increases tensile strength and elastic modulus in thedirections of stretch. It is most desirable for the amount of stretch ineach direction to be roughly equivalent, thereby providing similarproperties or behavior within the film or sheet when tested from anydirection.

[0115] The biaxial orientation may be obtained by any process known inthe art. However, tentering is preferred, wherein the material isstretched while heating in the transverse direction simultaneously with,or subsequent to, stretching in the machine direction.

[0116] Shrinkage can be controlled by holding the sheet in a stretchedposition and heating for a few seconds before quenching. This heatstabilizes the oriented film or sheet, which then may be forced toshrink only at temperatures above the heat stabilization temperature.

[0117] Film and Sheet Properties:

[0118] The properties exhibited by a film or sheet will depend onseveral factors indicated above, including the polymeric composition,the method of forming the polymer, the method of forming the film orsheet, and whether the film or sheet was treated for stretch orbiaxially oriented. These factors affect many properties of the film orsheet, such as shrinkage, tensile strength, elongation at break, impactstrength, dielectric strength and constant, tensile modulus, chemicalresistance, melting point, heat deflection temperature, and the like.

[0119] The film or sheet properties may be further adjusted by addingcertain additives and fillers to the polymeric composition, such ascolorants, dyes, UV and thermal stabilizers, antioxidants, plasticizers,lubricants antiblock agents, slip agents, and the like, as recitedabove. Alternatively, the polymeric materials which incorporatebis(2-hydroxyethyl)isosorbide of the present invention may be blendedwith one or more other polymers, such as starch, elastomers,polyolefins, polyesters, polyamides, nylons, and the like to improvecertain characteristics. Other polymers may be added to change suchcharacteristics as air permeability, optical clarity, strength and/orelasticity, for example.

[0120] Containers:

[0121] A further specific aspect of the present invention includesshaped articles in the form of containers produced from polymericmaterials which incorporate bis(2-hydroxyethyl)isosorbide. Saidpolymeric materials of the present invention which incorporatebis(2-hydroxyethyl)isosorbide and/or polyester polyols which incorporatebis(2-hydroxyethyl)isosorbide may include, for example, polyesters,polyamide esters, polyurethanes, polycarbonates, polycarbonate esters,polyether sulfones, polyether ketones and the like.

[0122] Plastic containers are widely used for foods and beverages, andalso for non-food materials. Poly(ethylene terephthalate) (PET) is usedto make many of these containers because of its appearance (opticalclarity), ease of blow molding, chemical and thermal stability, and itsprice. PET is generally fabricated into bottles by blow moldingprocesses, and generally by stretch blow molding.

[0123] In stretch blow molding, PET is first shaped by injection moldinginto a thick-walled preformed parison (a “preform”), which typically isin the shape of a tube with a threaded opening at the top. The parisonmay be cooled and then used later in a subsequent step, or the processmay be carried out in one machine with cooling just to the stretch blowmolding temperature. In the stretch blow molding step, the parison isheated to a high enough temperature in a mold to allow shaping, but notso hot that it crystallizes or melts (i.e., just above the glasstransition temperature Tg). The parison is expanded to fill the mold byrapidly stretching it mechanically in the axial direction (e.g.; byusing a mandrel) while simultaneously forcing air under pressure intothe heated parison to expand it radially. PET is typically modified forblow molding with a small amount of comonomer, usually1,4-cyclohexanedimethanol or isophthalic acid, which increases the widthof the temperature window for successful blow molding to about 9 C. Thecomonomer is necessary because of the need to have a wider temperaturewindow, and also to decrease the rate of stress induced crystallization.At the same time, the comonomer may have the undesirable effect oflowering the glass transition temperature and reducing the crystallinityof PET. Stretch blow molding of PET, and blow molding processes ingeneral, are well known in the art. Reviews are widely available, as forexample, “Blow Molding” by C. Irwin in Encyclopedia of Polymer ScienceAnd Engineering, Second Edition, Vol. 2, John Wiley and Sons, New York,1985, pp. 447-478.

[0124] The technology is widely used, but there are still improvementsthat need to be made. Containers which are derived from a renewableresource would be an improvement.

[0125] The containers described herein may be made by any method knownin the art, such as extrusion, injection molding, injection blowmolding, rotational molding, thermoforming of a sheet, and stretch-blowmolding.

[0126] In the present invention, the preferred method for molding acontainer is stretch-blow molding, which generally used in theproduction of poly(ethylene terephthalate) (PET) containers, such asbottles. In this case, use may be made of any of the cold parisonmethods, in which a preformed parison (generally made by injectionmolding) is taken out of the mold and then subjected to stretch blowmolding in a separate step. The hot parison method as known in the artmay also be used, wherein the hot parison is immediately subjected tostretch blow molding in the same equipment without complete coolingafter injection molding to make the parison. The parison temperaturewill vary based on the exact composition of the polymer to be used.Generally, parison temperatures in the range from about 90° C. to about160° C. are found useful. The stretch blow molding temperature will alsovary dependant on the exact material composition used, but a moldtemperature of about 80° C. to about 150° C. is generally found to beuseful.

[0127] Containers of the invention may have any shape desirable, andparticularly include narrow-mouth bottles and wide-mouth bottles havingthreaded tops and a volume of about 400 mL to about 3 liters, althoughsmaller and larger containers may be formed.

[0128] The containers can be used in standard cold fill applications.For some of the compositions of the present invention, hot fillapplications may also be used.

[0129] The containers of the invention are suitable for foods andbeverages, and other solids and liquids. The containers are normallyclear and transparent, but can be modified to have color or to beopaque, rather than transparent, if desired, by adding colorants ordyes, or by causing crystallization of the polymer, which results inopaqueness.

[0130] Fibers:

[0131] A further specific aspect of the present invention includesshaped articles in the form of fiber produced from polymeric materialswhich incorporate bis(2-hydroxyethyl)isosorbide. Said polymericmaterials of the present invention which incorporatebis(2-hydroxyethyl)isosorbide and/or polyester polyols which incorporatebis(2-hydroxyethyl)isosorbide may include, for example, polyesters,polyamide esters, polyurethanes, polycarbonates, polycarbonate esters,polyether sulfones, polyether ketones and the like.

[0132] Polyester fibers are produced in large quantities for use in avariety of applications. In particular, these fibers are desirable foruse in textiles, particularly in combination with natural fibers such ascotton and wool. Clothing, rugs, and other items may be fashioned fromthese fibers. Further, polyester fibers are desirable for use inindustrial applications due to their elasticity and strength. Inparticular, they are used to make articles such as tire cords and ropes.

[0133] The term “fibers” as used herein is meant to include continuousmonofilaments, non-twisted or entangled multifilament yarns, stapleyarns, spun yarns, and non-woven materials. Such fibers may be used toform uneven fabrics, knitted fabrics, fabric webs, or any otherfiber-containing structures, such as tire cords.

[0134] Synthetic fibers, such as nylon, acrylic, polyesters,polyurethanes, and others, are made by spinning and drawing the polymerinto a filament, which is then formed into a yarn by winding manyfilaments together. These fibers are often treated mechanically and/orchemically to impart desirable characteristics such as strength,elasticity, heat resistance, hand (feel of fabric), and the like asknown in the art based on the desired end product to be fashioned fromfibers.

[0135] The monomer composition of the polymeric materials whichincorporates bis(2-hydroxyethyl)isosorbide of the present invention isdesirably chosen to result in a partially crystalline polymer. Thecrystallinity is desirable for the formation of fibers, providingstrength and elasticity. As first produced, the polymeric material ismostly amorphous in structure. In preferred embodiments, the polymerreadily crystallizes on reheating and/or extension of the polymer.

[0136] In the process of the invention, fibers are made from the polymerby any process known in the art. Generally, however, melt spinning ispreferred for polymer fibers.

[0137] Melt spinning, which is most commonly used for polyesters, suchas poly(ethylene terephthalate), polyurethanes, and nylons comprisesheating the polymer to form a molten liquid, or melting the polymeragainst a heated surface. The molten polymer is forced through aspinneret with a plurality of fine holes. Upon contact with air or anon-reactive gas stream after passing through the spinneret, the polymersolution from each spinneret solidifies into filaments. The filamentsare gathered together downstream from the spinneret by a convergenceguide, and may be taken up by a roller or a plurality of rollers. Thisprocess allows filaments of various sizes and cross sections to beformed, including filaments having a round, elliptical, square,rectangular, lobed or dog-boned cross section, for example.

[0138] Following the extrusion and uptake of the fiber, the fiber isusually drawn, thereby increasing the crystallization and maximizingdesirable properties such as orientation along the longitudinal axis,which increases elasticity, and strength. The drawing may be done incombination with take-up by using a series of rollers, some of which aregenerally heated, as known in the art, or may be done as a separatestage in the process of fiber formation.

[0139] The polymer may be spun at speeds of from about 600 to 6000meters per minute or higher, depending on the desired fiber size. Fortextile applications, a fiber with a denier per filament of from about0.1 to about 100 is desired. Preferably, the denier is about 0.5 to 20,more preferably 0.7 to 10. However, for industrial applications thefiber should be from about 0.5 to 100 denier per filament, preferablyabout 1.0 to 10.0, most preferably 3.0 to 5.0 denier per filament. Therequired size and strength of a fiber can be readily be determined byone of ordinary skill in the art for any given application.

[0140] The resulting filamentary material is amenable to furtherprocessing through the use of additional processing equipment, or it maybe used directly in applications requiring a continuous filament textileyarn. If desired, the filamentary material subsequently may be convertedfrom a flat yarn to a textured yarn through known false twist texturingconditions or other processes known in the art. In particular, it isdesirable to increase the surface area of the fiber to provide a softerfeel and to enhance the ability of the fibers to breathe, therebyproviding better insulation and water retention in the case of textiles,for example. The fibers may therefore be crimped or twisted by the falsetwist method, air jet, edge crimp, gear crimp, or stuffer box, forexample. Alternatively, the fibers may be cut into shorter lengths,called staple, which may be processed into yarn. A skilled artisan candetermine the best method of crimping or twisting based on the desiredapplication and the composition of the fiber.

[0141] After formation, the fibers are finished by any methodappropriate to the desired final use. In the case of textiles, this mayinclude dyeing, sizing, or addition of chemical agents such asantistatic agents, flame retardants, UV light stabilizers, antioxidants,pigments, dyes, stain resistants, antimicrobial agents and the like,which are appropriate to adjust the look and hand of the fibers. Forindustrial applications, the fibers may be treated to impart additionaldesired characteristics such as strength, elasticity or shrinkage, forexample.

[0142] The continuous filament fiber of the invention may be used eitheras produced or texturized for use in a variety of applications such astextile fabrics for apparel and home furnishings, for example. Hightenacity fiber can be used in industrial applications such as highstrength fabrics, tarpaulins, sail cloth, sewing threads and rubberreinforcement for tires and V-belts, for example.

[0143] The staple fiber of the invention may be used to form a blendwith natural fibers, especially cotton and wool. In particular, thepolymeric materials form a chemically resistant fiber which is generallyresistant to mold, mildew, and other problems inherent to naturalfibers. The polymer fiber further provides strength and abrasionresistance and lowers the cost of material. Therefore, it is ideal foruse in textiles and other commercial applications, such as for use infabrics for apparel, home furnishings and carpets.

[0144] Further, the polymer of the invention may be used with anothersynthetic or natural polymer to form heterogeneous fiber, therebyproviding a fiber with improved properties. The heterogeneous fiber maybe formed in any suitable manner, such as side-by-side, sheath-core, andmatrix designs, as is known within the art.

[0145] Processes to produce polyurethane fibers are known within theart. See, for example, U.S. Pat. No. 6,096,252 and the references citedtherein.

[0146] Shaped Foamed Articles:

[0147] A further specific aspect of the present invention includesshaped foamed articles produced from the polymeric materials whichincorporate bis(2-hydroxyethyl)isosorbide. Said polymeric materials ofthe present invention which incorporate bis(2-hydroxyethyl)isosorbideand/or polyester polyols which incorporate bis(2-hydroxyethyl)isosorbidemay include, for example, polyesters, polyamide esters, polyurethanes,polycarbonates, polycarbonate esters, polyether sulfones, polyetherketones and the like.

[0148] Thermoplastic polymeric materials are foamed to provide lowdensity articles, such as films, cups, food trays, decorative ribbons,furniture parts and the like. For example, polystyrene beads containinglow boiling hydrocarbons, such as pentane, are formed into light weightfoamed cups for hot drinks such as coffee, tea, hot chocolate and thelike. Polypropylene can be extruded in the presence of blowing agentssuch as nitrogen or carbon dioxide gas to provide decorative films andribbons for package wrappings. Also, polypropylene can be injectionmolded in the presence of blowing agents to form lightweight furnitureparts such as table legs and to form lightweight chairs.

[0149] Polyesters, such as poly(ethylene terephthalate), typically havea much higher density, (e.g.; 1.3 g/cc), than other polymers. It would,therefore, be desirable to be able to foam polyester materials todecrease the weight of molded parts, films, sheets, food trays,thermoformed parts and the like. Such foamed articles also provideimproved insulating properties than unfoamed articles.

[0150] It has been generally been found in the art that the polyester tobe foamed should desirably have a high melt viscosity. This is desiredin order to have sufficient melt viscosity to hold the as formed foamedshape sufficiently long for the polyester to solidify to form the finalfoamed article. This can be achieved by raising the as producedpolyester inherent viscosity through post-polymerization processes, suchas the solid state polymerization method, as described above.Alternatively, the polyester may incorporate a branching agent, such asdescribed in U.S. Pat. Nos. 4,132,707, 4,145,466, 4,999,388, 5,000,991,5,110,844, 5,128,383, and 5,134,028. Such branched polyesters mayadditionally be subjected to the solid state polymerization, asdescribed above, to further enhance the melt viscosity. It has also beenfound that the incorporation of sulfonate substituents onto thepolyester backbone raise the apparent melt viscosity of the polyester,providing an adequately foamable polyester. More recently, it has beensuggested that such sulfonated polyesters may be reacted with divalentcations to enhance the melt viscosity even greater, allowing for moredesirable foamable polyesters, (see, for example, U.S. Pat. No.5,922,782).

[0151] The polyesters of the present invention may be readily foamed bya wide variety of methods. These include the injection of an inert gassuch as nitrogen or carbon dioxide into the melt during extrusion ormolding operations. Alternatively, inert hydrocarbon gases such asmethane, ethane, propane, butane, and pentane, or chlorofluorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, and the like may be used.Another method involves the dry blending of chemical blowing agents withthe polyester and then extruding or molding the compositions to providefoamed articles. During the extrusion or molding operation, an inert gassuch as nitrogen is released from the blowing agents and provides thefoaming action. Typical blowing agents include azodicarbonamide,hydrazocarbonamide, dinitrosopentamethylenetetramine, p-toluenesul fonylhydrazodicarboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxa-diazin-2-one,sodium borohydride, sodium bicarbonate, 5-phenyltetrazole,p,p′-oxybis(benzenesulfonylhydrazide) and the like. Still another methodinvolves the blending of sodium carbonate or sodium bicarbonate with oneportion of the polyester pellets, blending of an organic acid, such ascitric acid, with another portion of the polyester pellets and thenblending of the two types of pellets through extrusion or molding atelevated temperatures. Carbon dioxide gas is released from theinteraction of the sodium carbonate and citric acid to provide thedesired foaming action in the polymeric melt.

[0152] It is desirable that the foamable polyester compositionsincorporate nucleation agents to create sites for bubble initiation,influence the cell size of the foamed sheet or object and to hasten thesolidification of the as foamed article. Examples of said nucleationagents may include sodium acetate, talc, titanium dioxide, polyolefinmaterials such as polyethylene, polypropylene, and the like.

[0153] Polymeric foaming equipment and processes are generally knownwithin the art. See, for example, U.S. Pat. Nos. 5,116,881, 5,134,028,4,626,183, 5,128,383, 4,746,478, 5,110,844, 5,000,844, and 4,761,256.Additional reviews on foaming technology may be found in Kirk-OthmerEncyclopedia of Chemical Technology, Third Edition, Volume 11, pp.82-145 (1980), John Wiley and Sons, Inc., New York, N.Y. and theEncyclopedia of Polymer Science and Engineering, Second Edition, Volume2, pp. 434-446 (1985), John Wiley and Sons, Inc., New York, N.Y. Thesereferences are herein incorporated into the present invention.

[0154] As described above, the foamable polyester compositions mayinclude a wide variety of additives, fillers, or be blended with othermaterials. For biodegradable foams, the addition of starch, starchderivatives, cellulose and cellulose derivatives is especiallypreferred.

[0155] Polyurethane foams are known within the art. Representativereferences include, for example, U.S. Pat. Nos. 4,139,501, 4,284,730,4,317,889, 4,365,025, 4,374,207, 4,384,051, 4,451,588, 4,529,742,4,535,096, 4,668,708, 5,023,280, 5,059,633, 5,063,253, 5,100,925,5,270,348, 5,369,138, 5,397,811, 5,418,261, 5,506,278, 5,536,757,6,107,355, 6,114,402 6,114,403, 6,117,917, and the references citedtherein. Polyurethane foams of the present invention which incorporatebis(2-hydroxyethyl)isosorbide and/or polyester polyols which incorporatebis(2-hydroxyethyl)isosorbide may be produced by any known method in theart.

EXAMPLES

[0156] Test Methods:

[0157] Differential Scanning Calorimetry, (DSC), is performed on a TAInstruments Model Number 2920 machine. Samples are heated under anitrogen atmosphere at a rate of 20 degrees C./minute to 300 degrees C.,programmed cooled back to room temperature at a rate of 20 degreesC./minute and then reheated to 300 degrees C. at a rate of 20 degreesC./minute. The observed sample glass transition temperature, (Tg), andcrystalline melting temperature, (Tm), noted below were from the secondheat.

[0158] Inherent Viscosity, (IV), is defined in “Preparative Methods ofPolymer Chemistry”, W. R. Sorenson and T. W. Campbell, 1961, p. 35. Itis determined at a concentration of 0.5 g/100 mL of a 50:50 weightpercent trifluoroacetic acid:dichloromethane acid solvent system at roomtemperature by a Goodyear R-103B method.

[0159] Biodegradation is performed according to the ISO 14855 method:“Determination of the ultimate aerobic biodegradability anddisintegration of plastic materials under controlled compostingconditions—Method by analysis of evolved carbon”. This test involvedinjecting an inoculum consisting of a stabilized and mature compostderived from the organic fraction of municipal solid waste with groundpowder of the polymer to be tested, composting under standard conditionsat an incubation temperature controlled at 58° C.+/−2° C. The test isconducted with one polymer sample. The carbon dioxide evolved is used todetermine the extent of biodegradation.

Example 1

[0160] To a reactor is charged isosorbide, (146.14 grams), ethylenecarbonate, (184.93 grams), and potassium carbonate, (1.66 grams). Thereactor is purge with nitrogen and then is slowly heated with stirringto 150° C. with a slight nitrogen purge. The resulting, reaction mixtureis stirred at 150° C. with a slight nitrogen purge until the carbondioxide evolution ceases. The resulting reaction mixture is then stirredan additional hour at 150° C. with a slight nitrogen purge. Theresulting reaction product is allowed to cool to room temperature.

[0161] The as produced reaction product is purified through vacuumdistillation to provide the bis(2-hydroxyethyl)isosorbide product.

Example 2

[0162] To a 200 gallon autoclave is charged dimethyl terephthalate,(126.16 pounds), bis(2-hydroxyethyl)isosorbide, (152.11 pounds),manganese(II) acetate tetrahydrate, (37.65 grams), and antimony(III)trioxide, (13.6 grams). The autoclave is purged three times withnitrogen and heated to 245° C. over 4.5 hours with stirring. Over thisheating cycle, distillate is recovered. With continued heating andstirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum,(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0163] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

Comparative Example CE1

[0164] To a 200 gallon autoclave is charged dimethyl terephthalate,(126.16 pounds), isosorbide, (9.5 pounds), ethylene glycol, (73.4pounds), manganese(II) acetate tetrahydrate, (37.65 grams), andantimony(III) trioxide, (13.6 grams). The autoclave is purged threetimes with nitrogen and heated to 245° C. over 4.5 hours with stirring.Over this heating cycle, distillate is recovered. With continued heatingand stirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0165] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0166] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 2.5 mole percent isosorbide. This wouldsuggest that 50 percent of the added isosorbide is incorporated withinthe polymer.

Example 3

[0167] To a 200 gallon autoclave is charged dimethyl terephthalate,(126.16 pounds), bis(2-hydroxyethyl)isosorbide, (15.22 pounds), ethyleneglycol, (73.4 pounds), manganese(II) acetate tetrahydrate, (37.65grams), and antimony(III) trioxide, (13.6 grams). The autoclave ispurged three times with nitrogen and heated to 245° C. over 4.5 hourswith stirring. Over this heating cycle, distillate is recovered. Withcontinued heating and stirring, vacuum is staged onto the autoclave over1.5 hours. The resulting reaction mixture is stirred at 275° C. underfull vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. Thevacuum is then released and the resulting reaction mixture is extrudedout of the autoclave as a ribbon, the polymer ribbon is cooled andchopped.

[0168] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0169] The polymer is analyzed for composition with proton NMR and foundto essentially incorporated mole percent bis(2-hydroxyethyl)isosorbide.This would suggest that essentially 100 percent of the addedbis(2-hydroxyethyl)isosorbide is incorporated within the polymer.

[0170] The above prepared polymer of the present invention is found tohave essentially quantitative incorporation of thebis(2-hydroxyethyl)isosorbide monomer. This is twice the incorporationrate of the isosorbide monomer into comparable polymers such asComparative Example CE1.

Example 4

[0171] To a 200 gallon autoclave is charged dimethyl terephthalate,(98.4 pounds), dimethyl 5-sulfoisophthalate, sodium salt, (3.8 pounds),dimethyl glutarate, (20.8 pounds), bis(2-hydroxyethyl)isosorbide, (15.22pounds), ethylene glycol, (73.4 pounds), manganese(II) acetatetetrahydrate, (37.65 grams), and antimony(III) trioxide, (13.6 grams).The autoclave is purged three times with nitrogen and heated to 245° C.over 4.5 hours with stirring. Over this heating cycle, distillate isrecovered. With continued heating and stirring, vacuum is staged ontothe autoclave over 1.5 hours. The resulting reaction mixture is stirredat 275° C. under full vacuum (pressure equal to or less than 2 mm Hg)for 4 hours. The vacuum is then released and the resulting reactionmixture is extruded out of the autoclave as a ribbon, the polymer ribbonis cooled and chopped.

[0172] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0173] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 5 mole percent bis(2-hydroxyethyl)isosorbide.This would suggest that essentially 100 percent of the addedbis(2-hydroxyethyl)isosorbide is incorporated within the polymer.

[0174] The above prepared polymer is ground to powder and subjected to abiodegradation test as detailed above. This copolyester of the presentinvention is found to biodegrade.

Example 5

[0175] To a 200 gallon autoclave is charged dimethyl isophthalate,(126.11 pounds), bis(2-hydroxyethyl)isosorbide, (152.11 pounds),manganese(II) acetate tetrahydrate, (37.65 grams), and antimony(III)trioxide, (13.6 grams). The autoclave is purged three times withnitrogen and heated to 245° C. over 4.5 hours with stirring. Over thisheating cycle, distillate is recovered. With continued heating andstirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0176] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

Example 6

[0177] To a 200 gallon autoclave is charged dimethyl adipate, (113.2pounds), bis(2-hydroxyethyl)isosorbide, (15.22 pounds), ethylene glycol,(73.4 pounds), manganese(II) acetate tetrahydrate, (37.65 grams), andantimony(III) trioxide, (13.6 grams). The autoclave is purged threetimes with nitrogen and heated to 245° C. over 4.5 hours with stirring.Over this heating cycle, distillate is recovered. With continued heatingand stirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0178] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0179] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 5 mole percent bis(2-hydroxyethyl)isosorbide.This would suggest that essentially 100 percent of the addedbis(2-hydroxyethyl)isosorbide is incorporated within the polymer.

Example 7

[0180] To a 200 gallon autoclave is charged dimethyl2,6-naphthalenedicarboxylate, (158.68 pounds),bis(2-hydroxyethyl)isosorbide, (152.11 pounds), manganese(II) acetatetetrahydrate, (37.65 grams), and antimony(III) trioxide, (13.6 grams).The autoclave is purged three times with nitrogen and heated to 245° C.over 4.5 hours with stirring. Over this heating cycle, distillate isrecovered. With continued heating and stirring, vacuum is staged ontothe autoclave over 1.5 hours. The resulting reaction mixture is stirredat 275° C. under full vacuum (pressure equal to or less than 2 mm Hg)for 4 hours. The vacuum is then released and the resulting reactionmixture is extruded out of the autoclave as a ribbon, the polymer ribbonis cooled and chopped.

[0181] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

Example 8

[0182] To a 200 gallon autoclave is charged dimethyl terephthalate,(98.1 pounds), dimethyl 5-sulfoisophthalate, sodium salt, (3.8 pounds),dimethyl succinate, (19.0 pounds), trimethyl1,2,4-benzenetricarboxylate, (0.4 pounds),bis(2-hydroxyethyl)isosorbide, (15.2 pounds), ethylene glycol, (73.4pounds), manganese(II) acetate tetrahydrate, (37.65 grams), andantimony(III) trioxide, (13.6 grams). The autoclave is purged threetimes with nitrogen and heated to 245° C. over 4.5 hours with stirring.Over this heating cycle, distillate is recovered. With continued heatingand stirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum,(pressure equal to or less than 2 mm Hg), for 4 hours. The vacuum isthen released and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0183] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0184] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 5 mole percent bis(2-hydroxyethyl)isosorbide.This would suggest that essentially 100 percent of the addedbis(2-hydroxyethyl)isosorbide is incorporated within the polymer.

Example 9

[0185] To a 200 gallon autoclave is charged dimethyl terephthalate,(60.6 pounds), dimethyl adipate, (56.6 pounds),bis(2-hydroxyethyl)isosorbide, (29.83 pounds), ethylene glycol, (61.3pounds), manganese(II) acetate tetrahydrate, (37.65 grams), andantimony(III) trioxide, (13.6 grams). The autoclave is purged threetimes with nitrogen and heated to 245° C. over 4.5 hours with stirring.Over this heating cycle, distillate is recovered. With continued heatingand stirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0186] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0187] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 10 mole percentbis(2-hydroxyethyl)isosorbide. This would suggest that essentially 100percent of the added bis(2-hydroxyethyl)isosorbide is incorporatedwithin the polymer.

[0188] The above prepared polymer is ground to powder and subjected to abiodegradation test as detailed above. This copolyester of the presentinvention is found biodegrade.

Example 10

[0189] To a 200 gallon autoclave is charged dimethyl terephthalate,(73.8 pounds), dimethyl adipate, (22.6 pounds), isophthalic acid, (21.0pounds), bis(2-hydroxyethyl)isosorbide, (29.78 pounds), ethylene glycol,(61.3 pounds), manganese(II) acetate tetrahydrate, (37.65 grams), andantimony(III) trioxide, (13.6 grams). The autoclave is purged threetimes with nitrogen and heated to 245° C. over 4.5 hours with stirring.Over this heating cycle, distillate is recovered. With continued heatingand stirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0190] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0191] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 10 mole percent isosorbide. This wouldsuggest that essentially 100 percent of the addedbis(2-hydroxyethyl)isosorbide is incorporated within the polymer.

[0192] The above prepared polymer is ground to powder and subjected to abiodegradation test as detailed above. This copolyester of the presentinvention was found to biodegrade

[0193] 1.1 grams of this polymer of the present invention is dissolvedin 10.0 grams of tetrahydrofuran at room temperature. After mixing for 4hours at room temperature, a clear solution is obtained. The solution ispoured into a 2-inch diameter aluminum pan and allowed to dry at roomtemperature overnight. The resulting film is clear and pliable.

Example 11

[0194] To a 5 gallon autoclave is charged terephthalic acid, (14.9pounds), adipic acid, (3.4 pounds), bis(2-hydroxyethyl)isosorbide, (2.7pounds), ethylene glycol, (13.5 pounds), cobalt(II) acetatetetrahydrate, (1.83 grams), and antimony(III) trioxide, (3.10 grams).The polymerization autoclave is equipped with a fractional distillationcolumn and a stirrer. The autoclave is purged three times with nitrogen,closed under 50 psig of nitrogen pressure and heated to 265° C. over 5hours with stirring. The pressure rises to 70 psig during this time, asesterification takes place. At the end of this time period, the pressureis vented back to psig. Water and ethylene glycol distill from theautoclave. The temperature is maintained at 265° C. Within an hour, thecontents of the autoclave are a clear, viscous melt. The excess pressurein the autoclave is then vented. A solution of ethylene glycol andpolyphosphoric acid (3.45 weight percent phosphorous) is pumped into theautoclave. With continued heating and stirring, vacuum is staged ontothe autoclave. The autoclave is then heated to 275° C. The resultingreaction mixture is stirred at 275° C. under full vacuum (pressure equalto or less than 2 mm Hg), for 4 hours. The vacuum is then released andthe resulting reaction mixture is extruded out of the autoclave as aribbon, the polymer ribbon is cooled and chopped.

[0195] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g. This polymer istested for glass transition temperature by the above mentioned DSC test.

Example 12

[0196] To a 200 gallon autoclave is charged dimethyl2,6-naphthalenedicarboxylate, (92.1 pounds), dimethyl adipate, (45.3pounds), bis(2-hydroxyethyl)isosorbide, (30.4 pounds), ethylene glycol,(61.3 pounds), manganese(II) acetate tetrahydrate, (37.65 grams), andantimony(III) trioxide, (13.6 grams). The autoclave is purged threetimes with nitrogen and heated to 245° C. over 4.5 hours with stirring.Over this heating cycle, distillate is recovered. With continued heatingand stirring, vacuum is staged onto the autoclave over 1.5 hours. Theresulting reaction mixture is stirred at 275° C. under full vacuum(pressure equal to or less than 2 mm Hg) for 4 hours. The vacuum is thenreleased and the resulting reaction mixture is extruded out of theautoclave as a ribbon, the polymer ribbon is cooled and chopped.

[0197] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

Example 13

[0198] To a 200 gallon autoclave is charged dimethyl terephthalate,(60.6 pounds), dimethyl adipate, (56.6 pounds),bis(2-hydroxyethyl)isosorbide, (30.4 pounds), 1,4-butanediol, (75.0pounds), and titanium(IV) isopropoxide, (19.57 grams). The autoclave ispurged three times with nitrogen and heated to 245° C. over 4.5 hourswith stirring. Over this heating cycle, distillate is recovered. Withcontinued heating and stirring, vacuum is staged onto the autoclave over1.5 hours. The resulting reaction mixture is stirred at 255° C. underfull vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. Thevacuum is then released and the resulting reaction mixture is extrudedout of the autoclave as a ribbon, the polymer ribbon is cooled andchopped.

[0199] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

[0200] The above prepared polymer is ground to powder and subjected to abiodegradation test as detailed above. This copolyester of the presentinvention was found to biodegrade.

Example 14

[0201] To a 200 gallon autoclave is charged dimethyl terephthalate,(60.6 pounds), dimethyl adipate, (56.6 pounds),bis(2-hydroxyethyl)isosorbide, (30.4 pounds), 1,3-propanediol, (63.3pounds), and titanium(IV) isopropoxide, (19.57 grams). The autoclave ispurged three times with nitrogen and heated to 245° C. over 4.5 hourswith stirring. Over this heating cycle, distillate is recovered. Withcontinued heating and stirring, vacuum is staged onto the autoclave over1.5 hours. The resulting reaction mixture is stirred at 255° C. underfull vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. Thevacuum is then released and the resulting reaction mixture is extrudedout of the autoclave as a ribbon, the polymer ribbon is cooled andchopped.

[0202] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g.

Example 15

[0203] To a 200 gallon autoclave is charged dimethyl terephthalate,(126.16 pounds), bis(2-hydroxyethyl)isosorbide, (7.61 pounds), ethyleneglycol, (73.4 pounds), manganese(II) acetate tetrahydrate, (37.65grams), and antimony(III) trioxide, (13.6 grams). The autoclave ispurged three times with nitrogen and heated to 245° C. over 4.5 hourswith stirring. Over this heating cycle, distillate is recovered. Withcontinued heating and stirring, vacuum is staged onto the autoclave over1.5 hours. The resulting reaction mixture is stirred at 275° C. underfull vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. Thevacuum is then released and the resulting reaction mixture is extrudedout of the autoclave as a ribbon, the polymer ribbon is cooled andchopped.

[0204] The polymer is tested for inherent viscosity, as described aboveand is found to have an IV greater than 0.35 dL/g. Its Tg is found byDSC to be above the Tg of a comparative polyester without the isosorbidederivative.

[0205] The polymer is analyzed for composition with proton NMR and foundto essentially incorporate 2.5 mole percentbis(2-hydroxyethyl)isosorbide. This would suggest that essentially 100percent of the added bis(2-hydroxyethyl)isosorbide is incorporatedwithin the polymer.

Example 16

[0206] To a 2 liter three necked glass flask was added adipic acid,(438.42 grams), bis(2-hydroxyethyl)isosorbide, (234.14 grams),di(ethylene glycol), (106.12 grams), and 1,4-butanediol, (225.30 grams).With stirring, the reaction mixture was slowly heated to a finaltemperature of 200° C. under a slight nitrogen purge. Vacuum(pressure=10-15 mmHg) was applied while the reaction was stirring andheating were allowed to continue. Distillates were collected until amolecular weight of 2000 was achieved, as is measurable by the acidvalue (KOH mg/g). The resulting polyester polyol was allowed to cool toroom temperature.

Example 17

[0207] A reactor is charged with bis(2-hydroxyethyl)isosorbide, (234.14grams). The reaction mixture is heated to 70° C. with stirring under aslight nitrogen purge. Tolylene 2,6-diisocyanate, (174.16 grams), isdropwise added over 1 hour to the stirred reaction mixture at 70° C. Theresulting reaction mixture is allowed to stir for an additional hour at70° C. and then the resulting polyurethane product is allowed to cool toroom temperature and recovered.

Example 18

[0208] A reactor is charged with the polyester polyol prepared inExample 16, (200.00 grams). The reaction mixture is heated to 70° C.with stirring under a slight nitrogen purge. 4,4′-Methylenebis(phenylisocyanate), (25.03 grams), is dropwise added over 1 hour to the stirredreaction mixture at 70° C. The resulting reaction mixture is allowed tostir for an additional hour at 70° C. and then the resultingpolyurethane product is allowed to cool to room temperature andrecovered.

Example 19

[0209] The polymer of the present invention produced in Example 15,above, is extruded as a film using a Killion PL 100 Film extrusion line.The processing conditions are as follows: Extruder Barrel Temperaturezone 1 190° C. zone 2 270° C. zone 3 280° C. zone 4 280° C. Clamp ringtemperature 280° C. Adaptor temperature (inlet) 290° C. Melt pumptemperature 290° C. Melt pump rpm 10 Throughput 3 lb./hr. Adaptertemperature (outlet) 280° C. Extruder melt pressure ˜1500 psi Dieadapter temperature 290° C. Die temperature 290° C. Die Lip temperature290° C. Die gap 0.25 mm (10 mil) Die size 4-inch Casting temperature 50°C. Casting speed 5 & 3 in/min. Filter size 25 microns

[0210] The film exiting the die is 4 inches wide and 0.10 mm (4 mils)thick.

[0211] The extruded film is stretched uniaxially and biaxially using amodified Bruckner Stretching Frame (Bruckner, Siegsdorf, Germany). Thesample is inserted with the machine direction (MD) on the Y axis of themachine. Draw speed is 1.50 in/sec. Typical machine settings include;Plaque preheat temp=110° C., Shutter Close Temperature=115° C., andEmitter temperature=600° C. When a Draw ratio X (X 100%)=1 and a Drawratio Y (X 100%)=2 is performed on the as extruded film, the filmmodulus and elongation at break are both significantly improved overthat found for the unstretched film.

Example 20

[0212] The material produced in Example 15, above, is injection moldedinto discs (thickness ⅛ inch, diameter 4 inches) and tensile bars. A Boy30M (Boy Gmbh, Fernthalr, Germany) is used to injection mold the parts.The conditions used are as follows: Barrel temperature 280° C. Moldtemperature 50° C. Screw speed 210 rpm Injection speed 100% Injectionpressure 13 bar Hold pressure 12 bar Back pressure 3 bar Injection time2 seconds Cooling time 25 seconds

Example 21

[0213] The polymer produced in Example 3, above, is used to produce a 14mil thick sheet by extrusion using a film/sheet pilot line made by EganMachinery (Somerville, N.J.). The conditions for extrusion are asfollows: Extruder barrel temperatures Zone 1 255° C. Zone 2 255° C. Zone3 255° C. Zone 4 255° C. Zone 5 275° C. Zone 6 275° C. Melt line temp. 50° C. Die temp. 280° C. Roller 1  25° C. Roller 2  25° C. Roller 3 20° C.

[0214] The sheet is trimmed to 6 to 7 inches wide and approximately 11inches long. After heating in a rectangular retaining bracket at 165° C.in a convection oven until softening takes place, the sheet is vacuumthermoformed into 1½ inch and 2 inch deep room temperature molds todemonstrate ability to thermoform. The obtained containers are opticallyclear and mechanically robust.

Example 22

[0215] The polymers of the present invention produced in Examples 3 and15, above, are made into 460 mL jars on a commercial Nissei ASB100DHInjection Single Blow stretch-blow molding unit using a one-stagestretch-blow molding process, and using a 132.5 mm rod for the stretch.The polymer is injection molded at a melt temperature of 275° C. to makea preform, which is then subjected to the stretch-blow molding processat 100° C. in the same equipment without complete cooling.

Example 23

[0216] The polymer of the present invention produced in Example 15,above, is ground and dried at 130° C. overnight in a vacuum. Rods aremade from the polymer by first placing it in a mold which is then heatedunder gentle pressure from a plunger. The pressure is provided by ahydraulic press. When the polymer began to soften, more pressure(500-1000 lbs/in²) is applied to compress the polymer into a hard rod.The ingress of moisture is reduced by encasing the equipment in a Lucite® box which is continuously purged by a flow of dry nitrogen.

[0217] Spinning is immediately carried out on a single filament spinningmachine. The polymer is rod form is melted by pressing it against aheated “grid” which is conical in shape with a hole at the apex. Themachine temperatures are slowly raised until the melted polymer startsto flow through this hole. In the present example, this occurs atapproximately 270° C. The polymer is then filtered through a bed of80/120 shattered metal, and finally emerges from the single holespinneret capillary, 0.020 inch in diameter and 0.030 inch long. Thethroughput is 0.30 grams per minute (gpm), and the fiber, which is to bedrawn, is taken up at 50 meters per minute (mpm). These condition arefound to give low orientation single filaments of about 70 denier perfilament (dpf). A temperature scan is made to produce the optimum spunfiber for subsequent drawing. A fiber sample is also made at the maximumtake up speed possible in order to obtain a feel for the draw down andto measure the spun fiber properties.

[0218] Single filament drawing is performed on modular draw units withhot shoes between each roll. The fiber is drawn in two stages using thesecond stage to develop the maximum fiber tenacity and crystallinity. Inthis way, a single filament is collected and small samples cut from thelast roll. A sample is tested for its thermal properties by theabove-mentioned DSC method and for tensile properties using ASTM testmethod D3822. Its Tg is found by DSC to be above the Tg of a comparativepolyester fiber without the isosorbide derivative.

What is claimed is:
 1. Bis(2-hydroxyethyl)isosorbide.
 2. A polymercomposition comprising a polymer and bis(2-hydroxyethyl)isosorbidecomonomer.
 3. The polymer composition of claim 2 wherein the polymer isselected from the group consisting of polyester, polyamide ester,polyurethane, polycarbonate, polycarbonate ester, polyether sulfone,polyether ketone, and polyether ether ketone.
 4. The polymer compositionof claim 2 further comprising a dicarboxylic acid.
 5. The polymercomposition of claim 4 further comprising at least a second glycol. 6.The polymer composition of claim 2 or claim 4 further comprising atleast one polyfunctional branching agent.
 7. A polyester comprising: (a)45.0 to 50.0 mole percent of a dicarboxylic acid, (b) 0.1 to 50.0 molepercent of bis(2-hydroxyethyl)isosorbide, (c) 0 to 49.9 mole percent ofat least one additional glycol, and (d) 0 to 5.0 mole percent of atleast one polyfunctional branching agent.
 8. The polymer composition ofclaim 4, wherein said dicarboxylic acid is selected from the groupconsisting of unsubstituted and substituted aromatic, aliphatic,unsaturated, and acyclic dicarboxylic acids; and the lower alkyl estersof aromatic, aliphatic, unsaturated, and acyclic dicarboxylic acidshaving from 8 carbons to 36 carbons.
 9. The polymer composition of claim4 wherein said dicarboxylic acid is selected from the group consistingof terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethylisophthalate, 2,6-naphthalene dicarboxylic acid,dimethyl-2,6-naphthalate, metal salts of 5-sulfo-dimethylisophthalate,oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinicacid, dimethyl succinate, methylsuccinic acid, glutaric acid, dimethylglutarate, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid,dimethyl adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioicacid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate,sebacic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylicacid, undecanedioic acid, 1,12-dodecanedicarboxylic acid,hexadecanedioic acid, docosanedioic acid, tetracosanedioic acid, dimeracid, 1,4-cyclohexanedicarboxylic acid,dimethyl-1,4-cyclohexanedicarboxylate, 1,3-cyclohexanedicarboxylic acid,dimethyl-1,3-cyclohexanedicarboxylate, 1,1-cyclohexanediacetic acid,fumaric acid, maleic anhydride, maleic acid, hexahydrophthalic acid,phthalic acid, and combinations thereof.
 10. The polymer composition ofclaim 5 wherein said glycol is selected from the group consisting ofunsubstituted, substituted, straight chain, branched, cyclic aliphatic,aliphatic-aromatic and aromatic diols having from 2 carbon atoms to 36carbon atoms; and poly(alkylene ether) glycols with molecular weightsbetween about 250 to 4,000.
 11. The polymer composition of claim 5wherein said glycol is selected from the group consisting ethyleneglycol, 1,3-propanediol, 1,2-propanediol,1,2-butanediol, 1,3-butanediol,1,3-2-methylpropanediol, neopentyl glycol, 1,4-butanediol,1,3-hexanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol,1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,1,14-tetradecanediol, 1,16-hexadecanediol, dimer diol,4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane,1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene glycol),poly(ethylene ether) glycols, poly(butylene ether) glycols andcombinations thereof.
 12. A process for producingbis(2-hydroxyethyl)isosorbide comprising the steps of: (a) contactingisosorbide with a stoichiometric excess of ethylene carbonate in thepresence of a catalyst, (b) heating the product of step (a) gradually,with mixing, at a temperature sufficient to substantially evolve carbondioxide from said product, and (c) cooling the product of step (b) toambient temperature.
 13. The process of claim 12 wherein the temperatureis from 50° C. to 300° C.
 14. The process of claim 12 wherein thetemperature is from 75° C. to 200° C.
 15. The polymer composition ofclaim 3 wherein said polyester is biodegradable.
 16. A polyurethanecomprising: (a) 45.0 to 50.0 mole percent of polyisocyanate, (b) 0.1 to50.0 mole percent of bis(2-hydroxyethyl)isosorbide, (c) 0 to 49.9 molepercent of at least one additional glycol, and (d) 0 to 5.0 mole percentat least one polyester polyol.
 17. The polymer composition of claim 16,wherein the polyisocyanate is selected from unblocked polyisocyanatesand blocked isocyanates.
 18. The polymer composition of claim 17 whereinthe blocked isocyanate is chemically blocked with a compound selectedfrom the group consisting of methanol, oximes, lactams, imidazole, andphenols.
 19. The polymer composition of claim 17 wherein thepolyisocyanate is selected from the group consisting of diphenylmethanediisocyanate, toluene diisocyanate, xylene diisocyanate, phenylenediisocyanate, naphthalene diisocyanate, 4,4′-methylene-bis-(cyclohexylisocyanate), isophorone diisocyanate, 1,6-hexamethylene diisocyanate, abiuret from 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate,mixtures thereof.
 20. The polymer composition of claim 2 in the form ofa shaped article.
 21. The shaped article of claim 20 in the form of afilm, sheet, fiber, container or foamed article.